JPH0653766B2 - Method for producing modified diene polymer rubber - Google Patents
Method for producing modified diene polymer rubberInfo
- Publication number
- JPH0653766B2 JPH0653766B2 JP28709186A JP28709186A JPH0653766B2 JP H0653766 B2 JPH0653766 B2 JP H0653766B2 JP 28709186 A JP28709186 A JP 28709186A JP 28709186 A JP28709186 A JP 28709186A JP H0653766 B2 JPH0653766 B2 JP H0653766B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- added
- polymer rubber
- polymer
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims description 92
- 229920001971 elastomer Polymers 0.000 title claims description 83
- 239000005060 rubber Substances 0.000 title claims description 83
- 150000001993 dienes Chemical class 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 38
- 150000001340 alkali metals Chemical class 0.000 claims description 38
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 15
- 150000002828 nitro derivatives Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 32
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- -1 ether compound Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- LFHISGNCFUNFFM-UHFFFAOYSA-N chloropicrin Chemical compound [O-][N+](=O)C(Cl)(Cl)Cl LFHISGNCFUNFFM-UHFFFAOYSA-N 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- XWBDWELWBUWSNI-UHFFFAOYSA-N dimethyl 4-nitrobenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C([N+]([O-])=O)C=C1C(=O)OC XWBDWELWBUWSNI-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 125000002897 diene group Chemical group 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UXGRXJVMQSSUGS-UHFFFAOYSA-N 1,2-dinitroethane Chemical compound [O-][N+](=O)CC[N+]([O-])=O UXGRXJVMQSSUGS-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241000357292 Monodactylus Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- JFOIBTLTZWOAIC-UHFFFAOYSA-N (4-nitrophenyl) 2,2,2-trifluoroacetate Chemical compound [O-][N+](=O)C1=CC=C(OC(=O)C(F)(F)F)C=C1 JFOIBTLTZWOAIC-UHFFFAOYSA-N 0.000 description 1
- VMLIWHOMSDOONJ-ONEGZZNKSA-N (E)-2,3-dinitrobut-2-ene Chemical compound [O-][N+](=O)C(/C)=C(\C)[N+]([O-])=O VMLIWHOMSDOONJ-ONEGZZNKSA-N 0.000 description 1
- UTANVCZNJLPXGK-ONEGZZNKSA-N (e)-1-nitrobut-1-ene Chemical compound CC\C=C\[N+]([O-])=O UTANVCZNJLPXGK-ONEGZZNKSA-N 0.000 description 1
- PGQZCAQEOAEPDW-BQYQJAHWSA-N (e)-1-nitrooct-1-ene Chemical compound CCCCCC\C=C\[N+]([O-])=O PGQZCAQEOAEPDW-BQYQJAHWSA-N 0.000 description 1
- RIHXMHKNTLBIPJ-NSCUHMNNSA-N (e)-1-nitroprop-1-ene Chemical compound C\C=C\[N+]([O-])=O RIHXMHKNTLBIPJ-NSCUHMNNSA-N 0.000 description 1
- DAHZYRVPEHDLPG-ONEGZZNKSA-N (e)-2-nitrobut-2-ene Chemical compound C\C=C(/C)[N+]([O-])=O DAHZYRVPEHDLPG-ONEGZZNKSA-N 0.000 description 1
- KQIWPQXBIFDSMD-AATRIKPKSA-N (e)-3,4-dinitrohex-3-ene Chemical compound CC\C([N+]([O-])=O)=C(\CC)[N+]([O-])=O KQIWPQXBIFDSMD-AATRIKPKSA-N 0.000 description 1
- CZWSUVQCPWIYID-HWKANZROSA-N (e)-4-methyl-1-nitropent-1-ene Chemical compound CC(C)C\C=C\[N+]([O-])=O CZWSUVQCPWIYID-HWKANZROSA-N 0.000 description 1
- RNKVJTCBQRLSRY-UHFFFAOYSA-N 1,1-dibromo-1-nitroethane Chemical compound CC(Br)(Br)[N+]([O-])=O RNKVJTCBQRLSRY-UHFFFAOYSA-N 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- DNYOTMDPSXBJRJ-UHFFFAOYSA-N 1,1-dichloro-1-nitropropane Chemical compound CCC(Cl)(Cl)[N+]([O-])=O DNYOTMDPSXBJRJ-UHFFFAOYSA-N 0.000 description 1
- MYOKPSNMMVMHBI-UHFFFAOYSA-N 1,1-diethoxyethane;potassium Chemical compound [K].CCOC(C)OCC MYOKPSNMMVMHBI-UHFFFAOYSA-N 0.000 description 1
- LKKHEZBRRGJBGH-UHFFFAOYSA-N 1,1-dinitroethane Chemical compound [O-][N+](=O)C(C)[N+]([O-])=O LKKHEZBRRGJBGH-UHFFFAOYSA-N 0.000 description 1
- WOVMXXUUELNGSX-UHFFFAOYSA-N 1,1-dinitropentane Chemical compound CCCCC([N+]([O-])=O)[N+]([O-])=O WOVMXXUUELNGSX-UHFFFAOYSA-N 0.000 description 1
- DFHLCCWFLMSKJI-UHFFFAOYSA-N 1,1-dinitropropane Chemical compound CCC([N+]([O-])=O)[N+]([O-])=O DFHLCCWFLMSKJI-UHFFFAOYSA-N 0.000 description 1
- XLAJFSRYFUHAPW-UHFFFAOYSA-N 1,2,3,5-tetranitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C([N+]([O-])=O)C([N+]([O-])=O)=C1 XLAJFSRYFUHAPW-UHFFFAOYSA-N 0.000 description 1
- FQHFOGCNEKGMQX-UHFFFAOYSA-N 1,2,3-triiodo-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(I)=C(I)C(I)=C1 FQHFOGCNEKGMQX-UHFFFAOYSA-N 0.000 description 1
- ONOWMDPHGJEBAZ-UHFFFAOYSA-N 1,2,3-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O ONOWMDPHGJEBAZ-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- GILZVDSAZMTLBE-UHFFFAOYSA-N 1,2,4,5-tetranitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C([N+]([O-])=O)C=C1[N+]([O-])=O GILZVDSAZMTLBE-UHFFFAOYSA-N 0.000 description 1
- IBRBMZRLVYKVRF-UHFFFAOYSA-N 1,2,4-trichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C=C1Cl IBRBMZRLVYKVRF-UHFFFAOYSA-N 0.000 description 1
- OJJRABFYHOHGGU-UHFFFAOYSA-N 1,2,4-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1 OJJRABFYHOHGGU-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- LPOQWSWPRAGSBK-UHFFFAOYSA-N 1,2-dibromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1Br LPOQWSWPRAGSBK-UHFFFAOYSA-N 0.000 description 1
- DLLDRYLYVHKDKK-UHFFFAOYSA-N 1,2-dibromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C(Br)=C1 DLLDRYLYVHKDKK-UHFFFAOYSA-N 0.000 description 1
- IGSAVPVCQHAPSM-UHFFFAOYSA-N 1,2-dichloro-4,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C=C1[N+]([O-])=O IGSAVPVCQHAPSM-UHFFFAOYSA-N 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- BYNQDIUAOQPBRK-UHFFFAOYSA-N 1,2-dimethyl-1-nitrocyclohexane Chemical compound CC1CCCCC1(C)[N+]([O-])=O BYNQDIUAOQPBRK-UHFFFAOYSA-N 0.000 description 1
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- HRJHFRXVXJFQFD-UHFFFAOYSA-N 1,2-dinitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1[N+]([O-])=O HRJHFRXVXJFQFD-UHFFFAOYSA-N 0.000 description 1
- XNKFCDGEFCOQOM-UHFFFAOYSA-N 1,2-dinitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C21 XNKFCDGEFCOQOM-UHFFFAOYSA-N 0.000 description 1
- ZWECFKSVQNZDSP-UHFFFAOYSA-N 1,2-dinitropropane Chemical compound [O-][N+](=O)C(C)C[N+]([O-])=O ZWECFKSVQNZDSP-UHFFFAOYSA-N 0.000 description 1
- PVRGPKACTCJCBF-UHFFFAOYSA-N 1,3,5-tribromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Br)C=C(Br)C=C1Br PVRGPKACTCJCBF-UHFFFAOYSA-N 0.000 description 1
- JCMBWDZBURXGMC-UHFFFAOYSA-N 1,3,6-trinitronaphthalene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC2=CC([N+](=O)[O-])=CC=C21 JCMBWDZBURXGMC-UHFFFAOYSA-N 0.000 description 1
- HATHNBZPXBWLFB-UHFFFAOYSA-N 1,3-dibromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Br)C=CC=C1Br HATHNBZPXBWLFB-UHFFFAOYSA-N 0.000 description 1
- RNABGKOKSBUFHW-UHFFFAOYSA-N 1,3-dichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(Cl)=C1 RNABGKOKSBUFHW-UHFFFAOYSA-N 0.000 description 1
- UNQYUXGLJGCUOE-UHFFFAOYSA-N 1,3-dimethyl-1-nitrocyclohexane Chemical compound CC1CCCC(C)([N+]([O-])=O)C1 UNQYUXGLJGCUOE-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- ITUGOFFBEXBDGZ-UHFFFAOYSA-N 1,3-dinitropropane Chemical compound [O-][N+](=O)CCC[N+]([O-])=O ITUGOFFBEXBDGZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QHTZEKUEAHGFIS-UHFFFAOYSA-N 1,4-dibromo-2,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Br)=C([N+]([O-])=O)C=C1Br QHTZEKUEAHGFIS-UHFFFAOYSA-N 0.000 description 1
- RZKKOBGFCAHLCZ-UHFFFAOYSA-N 1,4-dichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC=C1Cl RZKKOBGFCAHLCZ-UHFFFAOYSA-N 0.000 description 1
- HTFFTNQNCNUSOJ-UHFFFAOYSA-N 1,4-dimethyl-1-nitrocyclohexane Chemical compound CC1CCC(C)([N+]([O-])=O)CC1 HTFFTNQNCNUSOJ-UHFFFAOYSA-N 0.000 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- KWFGJLCFMKVZLQ-UHFFFAOYSA-N 1,4-dinitrobutane Chemical compound [O-][N+](=O)CCCC[N+]([O-])=O KWFGJLCFMKVZLQ-UHFFFAOYSA-N 0.000 description 1
- HYQUWYMJSAPGDY-UHFFFAOYSA-N 1,5-dibromo-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Br)C=C1Br HYQUWYMJSAPGDY-UHFFFAOYSA-N 0.000 description 1
- ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 1,5-dichloro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C=C1Cl ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 0.000 description 1
- VILFTWLXLYIEMV-UHFFFAOYSA-N 1,5-difluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(F)C=C1F VILFTWLXLYIEMV-UHFFFAOYSA-N 0.000 description 1
- KGAXNYXMWAYHFZ-UHFFFAOYSA-N 1,5-dinitropentan-3-one Chemical compound [N+](=O)([O-])CCC(=O)CC[N+](=O)[O-] KGAXNYXMWAYHFZ-UHFFFAOYSA-N 0.000 description 1
- OQCOYCBADKYRQS-UHFFFAOYSA-N 1,5-dinitropentane Chemical compound [O-][N+](=O)CCCCC[N+]([O-])=O OQCOYCBADKYRQS-UHFFFAOYSA-N 0.000 description 1
- YXBHCFHBPVLHEZ-UHFFFAOYSA-N 1,6-dinitrohexane Chemical compound [O-][N+](=O)CCCCCC[N+]([O-])=O YXBHCFHBPVLHEZ-UHFFFAOYSA-N 0.000 description 1
- FKCMPAUACZEQFJ-UHFFFAOYSA-N 1-(2-nitroethoxy)propane Chemical compound CCCOCC[N+]([O-])=O FKCMPAUACZEQFJ-UHFFFAOYSA-N 0.000 description 1
- KEELANLBFIOZSH-UHFFFAOYSA-N 1-(nitromethyl)cyclohexene Chemical compound [O-][N+](=O)CC1=CCCCC1 KEELANLBFIOZSH-UHFFFAOYSA-N 0.000 description 1
- RPGQJXGITZORAG-UHFFFAOYSA-N 1-(nitromethyl)naphthalene Chemical compound C1=CC=C2C(C[N+](=O)[O-])=CC=CC2=C1 RPGQJXGITZORAG-UHFFFAOYSA-N 0.000 description 1
- JXRGVYLCDXJWLY-UHFFFAOYSA-N 1-bromo-1-nitrocyclohexane Chemical compound [O-][N+](=O)C1(Br)CCCCC1 JXRGVYLCDXJWLY-UHFFFAOYSA-N 0.000 description 1
- AMGDESQTWHNCTP-UHFFFAOYSA-N 1-bromo-1-nitroethane Chemical compound CC(Br)[N+]([O-])=O AMGDESQTWHNCTP-UHFFFAOYSA-N 0.000 description 1
- CGLRMJMKUHEFQB-UHFFFAOYSA-N 1-bromo-1-nitropropane Chemical compound CCC(Br)[N+]([O-])=O CGLRMJMKUHEFQB-UHFFFAOYSA-N 0.000 description 1
- HIMGPQVBNICCGL-UHFFFAOYSA-N 1-bromo-2-methyl-4-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1Br HIMGPQVBNICCGL-UHFFFAOYSA-N 0.000 description 1
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RFVYQWYNYFCXQL-UHFFFAOYSA-N C1=CC=CC2=CC([Li])=CC=C21 Chemical compound C1=CC=CC2=CC([Li])=CC=C21 RFVYQWYNYFCXQL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- NYTOUQBROMCLBJ-UHFFFAOYSA-N Tetranitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O NYTOUQBROMCLBJ-UHFFFAOYSA-N 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- LFASRCHQAYIROH-UHFFFAOYSA-N [Li]C1CCCC1 Chemical compound [Li]C1CCCC1 LFASRCHQAYIROH-UHFFFAOYSA-N 0.000 description 1
- ZEDXYOJKIFJKHK-UHFFFAOYSA-N [Li]CCCCC1=CC=CC=C1 Chemical compound [Li]CCCCC1=CC=CC=C1 ZEDXYOJKIFJKHK-UHFFFAOYSA-N 0.000 description 1
- SHJXVDAAVHAKFB-UHFFFAOYSA-N [Li]CCCCCCCCCC Chemical compound [Li]CCCCCCCCCC SHJXVDAAVHAKFB-UHFFFAOYSA-N 0.000 description 1
- VBSKMKYTRASRSY-UHFFFAOYSA-N [Li]c1ccccc1CCCC Chemical compound [Li]c1ccccc1CCCC VBSKMKYTRASRSY-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- DNPRVXJGNANVCZ-UHFFFAOYSA-N bromo(nitro)methane Chemical compound [O-][N+](=O)CBr DNPRVXJGNANVCZ-UHFFFAOYSA-N 0.000 description 1
- KWSSHZBBUQSMKF-UHFFFAOYSA-N bromo(trinitro)methane Chemical compound [O-][N+](=O)C(Br)([N+]([O-])=O)[N+]([O-])=O KWSSHZBBUQSMKF-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- CGKPGVZMSKVVOF-UHFFFAOYSA-N chloro(nitro)methane Chemical compound [O-][N+](=O)CCl CGKPGVZMSKVVOF-UHFFFAOYSA-N 0.000 description 1
- GNZCDDDPGSFZFG-UHFFFAOYSA-N chloro(trinitro)methane Chemical compound [O-][N+](=O)C(Cl)([N+]([O-])=O)[N+]([O-])=O GNZCDDDPGSFZFG-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- MLQMIKSBTAZNBK-UHFFFAOYSA-N dimethyl 3-nitrobenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC([N+]([O-])=O)=C1C(=O)OC MLQMIKSBTAZNBK-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- DWCLXOREGBLXTD-UHFFFAOYSA-N dmdnb Chemical compound [O-][N+](=O)C(C)(C)C(C)(C)[N+]([O-])=O DWCLXOREGBLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CMVIALRRHVVWIW-UHFFFAOYSA-N ethyl 2,2-bis(2,4-dinitrophenyl)acetate Chemical compound C=1C=C([N+]([O-])=O)C=C([N+]([O-])=O)C=1C(C(=O)OCC)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CMVIALRRHVVWIW-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- CCAKQXWHJIKAST-UHFFFAOYSA-N hexanitroethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)([N+]([O-])=O)C([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O CCAKQXWHJIKAST-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- PVYWOZWHSJHJFC-UHFFFAOYSA-N iodo(trinitro)methane Chemical compound [O-][N+](=O)C(I)([N+]([O-])=O)[N+]([O-])=O PVYWOZWHSJHJFC-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- CJSZWOGCKKDSJG-UHFFFAOYSA-N nitrocyclopentane Chemical compound [O-][N+](=O)C1CCCC1 CJSZWOGCKKDSJG-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- RPMXALUWKZHYOV-UHFFFAOYSA-N nitroethene Chemical group [O-][N+](=O)C=C RPMXALUWKZHYOV-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- XYXAUWIWPPUGLW-UHFFFAOYSA-N nitromethylcyclohexane Chemical compound [O-][N+](=O)CC1CCCCC1 XYXAUWIWPPUGLW-UHFFFAOYSA-N 0.000 description 1
- CXZVGALTVBHTKR-UHFFFAOYSA-N nitromethylcyclopentane Chemical compound [O-][N+](=O)CC1CCCC1 CXZVGALTVBHTKR-UHFFFAOYSA-N 0.000 description 1
- CAZVNFHXWQYGPD-UHFFFAOYSA-N oxolane;potassium Chemical compound [K].C1CCOC1 CAZVNFHXWQYGPD-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- LZGVDNRJCGPNDS-UHFFFAOYSA-N trinitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)[N+]([O-])=O LZGVDNRJCGPNDS-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は変性ジエン系重合体ゴムの製造方法に関するも
のであり、より詳しくは活性なアルカリ金属末端を有す
るジエン系重合体又はアルカリ金属が付加された共役ジ
エン系重合体ゴムとニトロ化合物とを反応させることを
特徴とする変性ジエン系重合体ゴムの製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to a method for producing a modified diene polymer rubber, more specifically, a diene polymer having an active alkali metal terminal or an alkali metal addition The present invention relates to a method for producing a modified diene-based polymer rubber, which comprises reacting the conjugated diene-based polymer rubber and a nitro compound.
＜従来の技術＞ 従来からポリブタジエンやブタジエン−スチレン共重合
体ゴム等の共役ジエン系重合体ゴムは自動車タイヤトレ
ッド用ゴムとして使用されてきたが、近年自動車の低燃
費化の要求と雪上及び氷上での走行安全性の要求から自
動車タイヤトレッド用ゴムとして転動抵抗が小さく、雪
上及び氷上での路面グリップの大きいゴム材料が望まれ
てきている。<Prior Art> Conventionally, conjugated diene polymer rubbers such as polybutadiene and butadiene-styrene copolymer rubber have been used as rubbers for automobile tire treads, but in recent years, there has been a demand for low fuel consumption of automobiles and snow and ice. Due to the requirement of driving safety, a rubber material having a small rolling resistance and a large road surface grip on snow and ice has been desired as a rubber for an automobile tire tread.
転動抵抗は重合体の反撥弾性と相関があり反撥弾性が高
くなると転動抵抗は小さくなる。The rolling resistance correlates with the impact resilience of the polymer, and the higher the impact resilience, the smaller the rolling resistance.
一方、雪上及び氷上での路面グリップは低温におけるＪ
ＩＳ硬度と相関があり、低温におけるＪＩＳ硬度が低い
ほど雪上及び氷上での路面グリップは大きくなることが
知られている。然るに既存のゴム材料においては、これ
ら特性は、実用上不満足であった。On the other hand, the road grip on snow and ice is
It is known that there is a correlation with the IS hardness, and the lower the JIS hardness at low temperature, the greater the road surface grip on snow and ice. However, in the existing rubber material, these characteristics were not practically satisfactory.
＜発明が解決しようとする問題点＞ 本発明の目的は、反撥弾性を高め、低温でのＪＩＳ硬度
を低減するジエン系重合体ゴムの改質方法を提供するこ
とにある。<Problems to be Solved by the Invention> An object of the present invention is to provide a method for modifying a diene polymer rubber that enhances impact resilience and reduces JIS hardness at low temperatures.
＜問題点を解決するための手段＞ 本発明者らは共役ジエン系重合体ゴムの反撥弾性を高
め、かつ低温でのＪＩＳ硬度を低くすべく鋭意研究を重
ねた結果、アルカリ金属含有ジエン系重合体と特定の化
合物とを反応させ、特定の原子団を重合体中に導入する
ことにより前記の目的が達せられることを見い出し本発
明を完成するに到った。<Means for Solving the Problems> The inventors of the present invention have conducted extensive studies to improve the impact resilience of the conjugated diene polymer rubber and to reduce the JIS hardness at low temperature. The present invention has been completed by finding that the above object can be achieved by reacting the combination with a specific compound and introducing a specific atomic group into the polymer.
すなわち、本発明は、 炭化水素溶媒中で共役ジエンモノマーもしくは共役ジエ
ンモノマーと芳香族ビニルモノマーとをアルカリ金属系
触媒を用いて重合を行うことにより得られるアルカリ金
属末端を有する活性共役ジエン系重合体ゴム、または、
炭化水素溶媒中で重合体鎖中に共役ジエン単位を有する
ジエン系重合体ゴムとアルカリ金属系触媒とを反応させ
ることにより得られるアルカリ金属が付加された共役ジ
エン系重合体ゴムに対して、ニトロ化合物を反応させて
なることを特徴とする変性ジエン系重合体ゴムの製造方
法に関するものである。That is, the present invention is an active conjugated diene-based polymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an alkali metal-based catalyst. Rubber or
For a conjugated diene-based polymer rubber to which an alkali metal has been added, which is obtained by reacting a diene-based polymer rubber having a conjugated diene unit in a polymer chain in a hydrocarbon solvent with an alkali metal-based catalyst, The present invention relates to a method for producing a modified diene polymer rubber, which comprises reacting a compound.
本発明で使用するアルカリ金属含有ジエン系重合体と
は、ジエン系単量体あるいは該単量体及びこれと共重合
可能な他の単量体をアルカリ金属基材触媒を用いて重合
して得られるアルカリ金属がジエン系重合体末端に結合
したもの、または及び重合方法（例えば溶液重合、乳化
重合など）の如何を問わず、重合体鎖中に共役ジエン単
位を有するジエン系重合体に後からの反応でアルカリ金
属を付加させたものをいう。The alkali metal-containing diene polymer used in the present invention is obtained by polymerizing a diene monomer or the monomer and another monomer copolymerizable therewith with an alkali metal-based catalyst. Regardless of the type of alkali metal bound to the end of the diene polymer, and the polymerization method (eg, solution polymerization, emulsion polymerization, etc.), a diene polymer having a conjugated diene unit in the polymer chain is later formed. The one to which an alkali metal is added in the reaction of.
ジエン系重合体ゴムとしては、１，３−ブタジエン、イ
ソプレン、１，３−ペンタジエン（ピペリレン）、２，
３−ジメチル−１，３−ブタジエン、１，３−ヘキサジ
エンなどの共役ジエンモノマーの重合体もしくは共重合
体ゴム、または共役ジエンモノマーと該モノマーと共重
合可能なスチレン、α−メチルスチレン、ビニルトルエ
ン、ビニルナフタレン、ジビニルベンゼン、トリビニル
ベンゼン、ジビニルナフタレンなどの芳香族ビニル化合
物、アクリロニトリルなどの不飽和ニトリル、（メタ）
アクリル酸のエステル類もしくはビニルピリジンなどと
の共重合体ゴムが挙げられるが、これらに限定されるも
のではない。Examples of the diene polymer rubber include 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,
Polymer or copolymer rubber of conjugated diene monomer such as 3-dimethyl-1,3-butadiene and 1,3-hexadiene, or styrene, α-methylstyrene, vinyltoluene copolymerizable with the conjugated diene monomer and the monomer , Vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and other aromatic vinyl compounds, acrylonitrile and other unsaturated nitriles, (meth)
Examples thereof include, but are not limited to, a copolymer rubber with an ester of acrylic acid or vinyl pyridine.
具体的にはポリブタジエンゴム、ポリイソプレンゴム、
ブタジエン−イソプレン共重合体ゴム、ブタジエン−ス
チレン共重合体ゴムなどが例示できる。Specifically, polybutadiene rubber, polyisoprene rubber,
Examples thereof include butadiene-isoprene copolymer rubber and butadiene-styrene copolymer rubber.
ジエン系重合体ゴムの末端にアルカリ金属が結合したジ
エン系重合体ゴムとは、前述のとおり、ジエン系重合体
ゴムをアルカリ金属基材触媒で重合して得たもので、重
合体鎖の少なくとも一端にアルカリ金属が結合した、重
合停止前のリビング重合体である。アルカリ金属基材触
媒、重合溶剤、ランダマイザー、共役ジエン単位のミク
ロ構造調節剤など通常使用されているものを用いること
が可能であり、該重合体の製造方法は特に制約は受けな
い。The diene polymer rubber in which an alkali metal is bonded to the end of the diene polymer rubber is, as described above, obtained by polymerizing the diene polymer rubber with an alkali metal-based catalyst, and at least the polymer chain. It is a living polymer before the termination of polymerization, in which an alkali metal is bonded to one end. It is possible to use a commonly used one such as an alkali metal-based catalyst, a polymerization solvent, a randomizer, a microstructure modifier for conjugated diene units, and the method for producing the polymer is not particularly limited.
ジエン系重合体ゴムにアルカリ金属を付加させたジエン
系重合体ゴムとは、アルカリ金属基材触媒、アルカリ土
類金属基材触媒、Ziegler 系触媒などを用いた溶液重
合、レドックス型触媒等を用いた乳化重合など通常の重
合方法によって前記した共役ジエンモノマーあるいは共
役ジエンモノマーおよびこれと共重合可能なモノマーと
を重合又は共重合させて得られるジエン系共重合体ゴム
（具体的にはポリブタジエンゴム、ポリイソプレンゴ
ム、ブタジエン−スチレン共重合体ゴム、ブタジエン−
イソプレン共重合体ゴム、ポリペンタジエンゴム、ブタ
ジエン−ピペリレン共重合体ゴム、ブタジエン−プロピ
レン交互共重合体ゴムなどが例示されるが）にアルカリ
金属を付加させたものである。Diene polymer rubbers obtained by adding an alkali metal to diene polymer rubbers include alkali metal base catalysts, alkaline earth metal base catalysts, solution polymerization using Ziegler catalysts, redox type catalysts, etc. Diene copolymer rubber obtained by polymerizing or copolymerizing the conjugated diene monomer or the conjugated diene monomer and a monomer copolymerizable therewith by a usual polymerization method such as emulsion polymerization (specifically, polybutadiene rubber, Polyisoprene rubber, butadiene-styrene copolymer rubber, butadiene-
Examples thereof include isoprene copolymer rubber, polypentadiene rubber, butadiene-piperylene copolymer rubber, and butadiene-propylene alternating copolymer rubber), but with an alkali metal added thereto.
ジエン系重合体ゴムへのアルカリ金属付加は通常実施さ
れている方法が用いられ、例えばジエン系重合体ゴムを
炭化水素溶媒中で、通常のアルカリ金属基材触媒とエー
テル化合物、アミン化合物、ホスフィン化合物等の極性
化合物の存在下に３０〜１００℃の温度で数十分乃至数
十時間の条件で付加反応が行われる。アルカリ金属基材
触媒の使用量はジエン系重合体ゴム１００ｇ当たり通
常、0.1 〜10ミリモルの範囲でよく、0.1 ミリモル未満
では反撥弾性の向上は得られず、10ミリモルを超えると
重合体の架橋、切断等の副反応が生じ反撥弾性の向上に
寄与しない。Alkali metal addition to the diene polymer rubber may be carried out by a commonly used method. For example, a diene polymer rubber may be added to a hydrocarbon solvent in a conventional alkali metal base catalyst and an ether compound, an amine compound or a phosphine compound. The addition reaction is carried out in the presence of such a polar compound at a temperature of 30 to 100 ° C. for several tens of minutes to several ten hours. The amount of the alkali metal-based catalyst used is usually in the range of 0.1 to 10 mmol per 100 g of the diene polymer rubber. If the amount is less than 0.1 mmol, the impact resilience cannot be improved. Side reactions such as cutting occur and do not contribute to the improvement of impact resilience.
極性化合物はアルカリ金属基材触媒１モルに対して通常
0.1 〜10モル、好ましくは0.5 〜2 モルである。重合お
よび付加反応に使用されるアルカリ金属基材触媒を例示
するならば以下のとおりである。The polar compound is usually used for 1 mol of the alkali metal-based catalyst.
It is 0.1 to 10 mol, preferably 0.5 to 2 mol. An example of the alkali metal-based catalyst used in the polymerization and the addition reaction is as follows.
リチウム、ナトリウム、カリウム、ルビジウム、セシウ
ム金属またはこれらの炭化水素化合物又は極性化合物と
の錯体である。It is a complex with lithium, sodium, potassium, rubidium, cesium metal or their hydrocarbon compounds or polar compounds.
好ましくは、２〜２０個の炭素原子を有するリチウムま
たはナトリウム化合物である。Preferred are lithium or sodium compounds having 2 to 20 carbon atoms.
例えば、エチルリチウム、ｎ−プロピルリチウム、iso
−プロピルリチウム、ｎ−ブチルリチウム、sec −ブチ
ルリチウム、ｔ−オクテルリチウム、ｎ−デシルリチウ
ム、フェニルリチウム、２−ナフチルリチウム、２−ブ
チル−フェニルリチウム、４−フェニル−ブチルリチウ
ム、シクロヘキシルリチウム、４−シクロペンチルリチ
ウム、１，４−ジリチオ−ブテン−２、ナトリウムナフ
タレン、ナトリウビフェニル、カリウム−テトラヒドロ
フラン錯体、カリウムジエトキシエタン錯体、α−メチ
ルスチレンテトラマーのナトリウム塩等である。For example, ethyl lithium, n-propyl lithium, iso
-Propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, 4-cyclopentyl lithium, 1,4-dilithio-butene-2, sodium naphthalene, natriubiphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, sodium salt of α-methylstyrene tetramer and the like.
重合反応およびアルカリ金属付加反応は炭化水素溶剤ま
たはテトロヒドロフラン、テトラヒドロピラン、ジオキ
サンなどのアルカリ金属基材触媒を破壊しない溶剤中で
行われる。The polymerization reaction and the alkali metal addition reaction are carried out in a hydrocarbon solvent or a solvent that does not destroy the alkali metal-based catalyst such as tetrohydrofuran, tetrahydropyran and dioxane.
適当な炭化水素溶剤としては、脂肪族炭化水素、芳香族
炭化水素、脂環族炭化水素から選ばれ、特に炭素数２〜
１２個を有するプロパン、ｎ−ブタン、iso −ブタン、
ｎ−ペンタン、iso −ペンタン、ｎ−ヘキサン、シクロ
ヘキサン、プロペン、１−ブテン、iso −ブテン、トラ
ンス−２−ブテン、シス−２−ブテン、１−ペンテン、
２−ペンテン、１−ヘキセン、２−ヘキセン、ベンゼ
ン、トルエン、キシレン、エチルベンゼンなどが好まし
い。またこれらの溶剤は２種以上を混合して使用するこ
とができる。The suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, and particularly has 2 to 2 carbon atoms.
Propane having twelve, n-butane, iso-butane,
n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene,
2-Pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like are preferable. Further, these solvents can be used as a mixture of two or more kinds.
次に、本発明で使用する前記のアルカリ金属含有ジエン
系重合体ゴムに反応させる化合物は分子中にニトロ基を
有するニトロ化合物である。Next, the compound to be reacted with the above-mentioned alkali metal-containing diene polymer rubber used in the present invention is a nitro compound having a nitro group in the molecule.
このようなニトロ化合物の具体的例を以下に示す。Specific examples of such nitro compounds are shown below.
（１）脂肪族ニトロ化合物があげられる。(1) An aliphatic nitro compound can be mentioned.
その例としては、例えば、ニトロメタン、ニトロエタ
ン、１−ニトロプロパン、２−ニトロプロパン、１−ニ
トロ−ｎ−ブタン、２−ニトロ−ｎ−ブタン、２−メチ
ル−１−ニトロブタン、３−メチル−１−ニトロブタ
ン、２−メチル−２−ニトロブタン、１−ニトロ−ｎ−
ヘキサン、１−ニトロ−ｎ−ヘプタン、１−ニトロ−ｎ
−オクタン、２−ニトロ−ｎ−オクタン等のモノニトロ
パラフィン類、ニトロエチレン、１−ニトロ−１−プロ
ペン、２−ニトロプロペン、３−ニトロ−１−プロペ
ン、１−ニトロ−１−ブテン、２−ニトロ−２−ブテ
ン、１−ニトロ−２−メチル−１−プロペン、２−ニト
ロ−１−ブテン、２−ニトロ−１−ペンテン、３−ニト
ロ−１，３−ペンタジエン、２−ニトロ−３−メチル−
１，３−ブタジエン、１−ニトロ−４−メチル−１−ペ
ンテン、２−ニトロ−１−ヘキセン、２−ニトロ−１−
ヘプテン、１−ニトロ−１−オクテン、１−ニトロ−
２，４，４−トリメチル−１−オクテン等のモノニトロ
オレフィン類、クロルニトロメタン、ブロムニトロメタ
ン、１−クロル−１−ニトロエタン、１−ブロム−１−
ニトロエタン、２−クロル−１−ニトロエタン、１−ク
ロル−１−ニトロプロパン、１−ブロム−１−ニトロプ
ロパン、２−クロル−１−ニトロプロパン、３−クロル
−１−ニトロプロパン、１−クロル−２−ニトロプロパ
ン、１−ブロム−２−ニトロプロパン、２−クロル−２
−ニトロプロパン、１，１−ジクロル−１−ニトロエタ
ン、１，１−ジブロム−１−ニトロエタン、１，１−ジ
クロル−１−ニトロプロパン、１，１−ジブロム−１−
ニトロプロパン、クロルピクリン、ブロムピクリン等の
モノハロゲンニトロパラフィン類、メチル−２−ニトロ
エチルエーテル、エチル−２−ニトロエチルエーテル、
２−ニトロエチル−ｎ−プロピルエーテル、２−ニトロ
エチルイソプロピルエーテル、ｎ−ブチル−２−ニトロ
エチルエーテル、メチル−２−ニトロイソプロピルエー
テル、３−メトキシ−２−ニトロブタン、メチル−２−
ニトロプロピルエーテル、ｎ−ブチル−２−ニトロイソ
プロピルエーテル、エチルニトロ−tert−ブチルエーテ
ル等のモノニトロエーテル類、ニトロアセトン、４，４
−ジメチル−５−ニトロ−２ペンタノン、メチル−２−
ニトロエチルケトン等のモノニトロケトン類、１，１−
ジニトロエタン、１，１−ジニトロプロパン、２，２−
ジニトロプロパン、１，１−ジニトロペンタン、３，３
−ジニトロペンタン、１，２−ジニトロエタン、１，２
−ジニトロプロパン、１，２−ジニトロベタン、２，３
−ジニトロブタン、２−メチル−２，３−ジニトロプロ
パン、２，３−ジメチルジニトロブタン、１，３−ジニ
トロプロパン、１，４−ジニトロブタン、１，５−ジニ
トロペンタン、１，６−ジニトロヘキサン、２，２−ジ
メチル−１，３−ジニトロプロパン、テトロクロル−
１，２−ジニトロエタン、テトロブロム−１，２−ジニ
トロエタン等のジニトロパラフィン類、２，３−ジニト
ロ−２−ブテン、３，４−ジニトロ−３−ヘキセン等の
ジニトロオレフィン類、トリニトロメタン、１，１，１
−トリニトロエタン、クロルトリニトロメタン、ブロム
トリニトロメタン、ヨードトリニトロメタン、テトラニ
トロメタン、ヘキサニトロエタン等のポリニトロ化合物
があげられる。Examples thereof include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, 1-nitro-n-butane, 2-nitro-n-butane, 2-methyl-1-nitrobutane, 3-methyl-1. -Nitrobutane, 2-methyl-2-nitrobutane, 1-nitro-n-
Hexane, 1-nitro-n-heptane, 1-nitro-n
-Octane, mononitroparaffins such as 2-nitro-n-octane, nitroethylene, 1-nitro-1-propene, 2-nitropropene, 3-nitro-1-propene, 1-nitro-1-butene, 2 -Nitro-2-butene, 1-nitro-2-methyl-1-propene, 2-nitro-1-butene, 2-nitro-1-pentene, 3-nitro-1,3-pentadiene, 2-nitro-3 -Methyl-
1,3-Butadiene, 1-nitro-4-methyl-1-pentene, 2-nitro-1-hexene, 2-nitro-1-
Heptene, 1-nitro-1-octene, 1-nitro-
Mononitroolefins such as 2,4,4-trimethyl-1-octene, chloronitromethane, bromonitromethane, 1-chloro-1-nitroethane, 1-bromo-1-
Nitroethane, 2-chloro-1-nitroethane, 1-chloro-1-nitropropane, 1-bromo-1-nitropropane, 2-chloro-1-nitropropane, 3-chloro-1-nitropropane, 1-chloro- 2-nitropropane, 1-bromo-2-nitropropane, 2-chloro-2
-Nitropropane, 1,1-dichloro-1-nitroethane, 1,1-dibromo-1-nitroethane, 1,1-dichloro-1-nitropropane, 1,1-dibromo-1-
Monohalogen nitroparaffins such as nitropropane, chloropicrin, brompicrin, methyl-2-nitroethyl ether, ethyl-2-nitroethyl ether,
2-nitroethyl-n-propyl ether, 2-nitroethyl isopropyl ether, n-butyl-2-nitroethyl ether, methyl-2-nitroisopropyl ether, 3-methoxy-2-nitrobutane, methyl-2-
Mononitroethers such as nitropropyl ether, n-butyl-2-nitroisopropyl ether, ethylnitro-tert-butyl ether, nitroacetone, 4,4
-Dimethyl-5-nitro-2 pentanone, methyl-2-
Mononitroketones such as nitroethylketone, 1,1-
Dinitroethane, 1,1-dinitropropane, 2,2-
Dinitropropane, 1,1-dinitropentane, 3,3
-Dinitropentane, 1,2-dinitroethane, 1,2
-Dinitropropane, 1,2-dinitrobetane, 2,3
-Dinitrobutane, 2-methyl-2,3-dinitropropane, 2,3-dimethyldinitrobutane, 1,3-dinitropropane, 1,4-dinitrobutane, 1,5-dinitropentane, 1,6-dinitrohexane , 2,2-dimethyl-1,3-dinitropropane, tetrochlor-
Dinitroparaffins such as 1,2-dinitroethane and tetrobrom-1,2-dinitroethane, dinitroolefins such as 2,3-dinitro-2-butene and 3,4-dinitro-3-hexene, trinitromethane, 1 , 1, 1
-Polynitro compounds such as trinitroethane, chlorotrinitromethane, bromotrinitromethane, iodotrinitromethane, tetranitromethane and hexanitroethane.
（２）脂肪族ニトロ化合物があげられる。(2) Aliphatic nitro compounds can be mentioned.
その例としては、例えば、ニトロシクロペンタン、１−
メチル−１−ニトロシクロペンタン、１−メチル−２−
ニトロシクロペンタン、シクロペンチルニトロメタン、
ニトロシクロヘキサン、１−メチル−１−ニトロシクロ
ヘキサン、２−メチル−１−ニトロシクロヘキサン、４
−メチル−１−ニトロシクロヘキサン、１，２−ジメチ
ル−１−ニトロシクロヘキサン、１，３−ジメチル−１
−ニトロシクロヘキサン、１，４−ジメチル−１−ニト
ロシクロヘキサン、１−ブロム−１−ニトロシクロヘキ
サン、１，２−ジニトロシクロヘキサン、１−ニトロメ
チルシクロヘキサン、１−ニトロメチルシクロヘキセン
などがあげられる。Examples thereof include, for example, nitrocyclopentane, 1-
Methyl-1-nitrocyclopentane, 1-methyl-2-
Nitrocyclopentane, cyclopentylnitromethane,
Nitrocyclohexane, 1-methyl-1-nitrocyclohexane, 2-methyl-1-nitrocyclohexane, 4
-Methyl-1-nitrocyclohexane, 1,2-dimethyl-1-nitrocyclohexane, 1,3-dimethyl-1
-Nitrocyclohexane, 1,4-dimethyl-1-nitrocyclohexane, 1-bromo-1-nitrocyclohexane, 1,2-dinitrocyclohexane, 1-nitromethylcyclohexane, 1-nitromethylcyclohexene and the like can be mentioned.
（３）芳香族ニトロ化合物があげられる。(3) An aromatic nitro compound can be used.
その例としては、ニトロベンゼン、１−クロル−３−ニ
トロベンゾイルクロライド、ｐ−ニトロフェニル−トリ
フルオルアセテート、ｏ−ジニトロベンゼン、ｍ−ジニ
トロベンゼン、１，５−ジフルオル−２，４−ジニトロ
ベンゼン、３，５−ジニトロベンゾイルクロライド、ｐ
−ジニトロベンゼン、１，２，３−トリニトロベンゼ
ン、１，２，４−トリニトロベンゼン、１，３，５−ト
リニトロベンゼン、１，２，３，５−テトラニトロベン
ゼン、１，２，４，５−テトラニトロベンゼン、ｏ−フ
ルオルニトロベンゼン、ｍ−フルオルニトロベンゼン、
ｐ−フルオルニトロベンゼン、１−フルオル−２，４−
ジニトロベンゼン、ｏ−クロルニトロベンゼン、ｍ−ク
ロルニトロベンゼン、ｐ−クロルニトロベンゼン、１−
クロル−２，４−ジニトロベンゼン、１−クロル−２，
６−ジニトロベンゼン、１−クロル−３，４−ジニトロ
ベンゼン、１−クロル−２，４，６−トリニトロベンゼ
ン、３，４−ジクロルニトロベンゼン、３，５−ジクロ
ルニトロベンゼン、２，４−ジクロルニトロベンゼン、
２，５−ジクロルニトロベンゼン、４，５−ジクロル−
１，２−ジニトロベンゼン、４，６−ジクロル−１，３
−ジニトロベンゼン、２，５−ジクロル−１，３−ジニ
トロベンゼン、２，４，５−トリクロルニトロベンゼ
ン、２−クロル−４−ニトロトルエン、２−クロル−６
−ニトロトルエン、４−クロル−２−ニトロトルエン、
２−クロル３，４−ジニトロトルエン、２−クロル−
３，５−ジニトロトルエン、ｏ−ブロムニトロベンゼ
ン、ｍ−ブロムニトロベンゼン、ｐ−ブロムニトロベン
ゼン、１−ブロム−２，４−ジニトロベンゼン、１−ブ
ロム−３，４−ジニトロベンゼン、１−ブロム−２，
４，６−トリニトロベンゼン、２，３−ジブロムニトロ
ベンゼン、３，４−ジブロムニトロベンゼン、２，４−
ジブロムニトロベンゼン、２，６−ジブロムニトロベン
ゼン、４，６−ジブロム−１，３−ジニトロベンゼン、
２，５−ジブロム−１，４−ジニトロベンゼン、２，
４，６−トリブロムニトロベンゼン、２−ブロム−４−
ニトロトルエン、２−ブロム−５−ニトロトルエン、３
−ブロム−２−ニトロトルエン、３−ブロム−４−ニト
ロトルエン、ｏ−ヨードニトロベンゼン、ｍ−ヨードニ
トロベンゼン、１−ヨード−２，４−ジニトロベンゼ
ン、１−ヨード−３，４−ジニトロベンゼン、３，４，
５−トリヨードニトロベンゼン、１−ニトロナフタリ
ン、２−ニトロナフタリン、ジニトロナフタリン類、ト
リニトロナフタリン類、テトラニトロナフタリン類、ニ
トロメチルナフタレン類、ニトロフェニルナフタレン
類、ハロニトロナフタレン類、ハロジニトロナフタレン
類、５−ニトロテトラリン、６−ニトロテトラリン、
５，６−ジニトロテトラリン、５，７−ジニトロテトラ
リン、５，８−ジニトロテトラリン、６，７−ジニトロ
テトラリン、３−ニトロ−１，２−ナフトキノン、７−
ニトロ−１，２−ナフトキノン、３−メチル−２−ニト
ロ−１，４−ナフトキノン、４−クロル−３−ニトロ−
１，２−ナフトキノン、２，３−ジクロル−５−ニトロ
−１，４−ナフトキノン、ニトロアントラキノン、ｐ−
ニトロフタル酸ジメチル、４，４′−ジニトロジフェニ
ル、４，４′−ジニトロジフェニルメタン、エチルビス
（２，４−ジニトロフェニル）アセテートなどがあげら
れる。Examples thereof include nitrobenzene, 1-chloro-3-nitrobenzoyl chloride, p-nitrophenyl-trifluoroacetate, o-dinitrobenzene, m-dinitrobenzene, 1,5-difluoro-2,4-dinitrobenzene, 3 , 5-dinitrobenzoyl chloride, p
-Dinitrobenzene, 1,2,3-trinitrobenzene, 1,2,4-trinitrobenzene, 1,3,5-trinitrobenzene, 1,2,3,5-tetranitrobenzene, 1,2,4,5- Tetranitrobenzene, o-fluoronitrobenzene, m-fluoronitrobenzene,
p-fluoronitrobenzene, 1-fluoro-2,4-
Dinitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, 1-
Chlor-2,4-dinitrobenzene, 1-chloro-2,
6-dinitrobenzene, 1-chloro-3,4-dinitrobenzene, 1-chloro-2,4,6-trinitrobenzene, 3,4-dichloronitrobenzene, 3,5-dichloronitrobenzene, 2,4-dinitrobenzene Chloronitrobenzene,
2,5-dichloronitrobenzene, 4,5-dichloro-
1,2-dinitrobenzene, 4,6-dichloro-1,3
-Dinitrobenzene, 2,5-dichloro-1,3-dinitrobenzene, 2,4,5-trichloronitrobenzene, 2-chloro-4-nitrotoluene, 2-chloro-6
-Nitrotoluene, 4-chloro-2-nitrotoluene,
2-chloro-3,4-dinitrotoluene, 2-chloro-
3,5-dinitrotoluene, o-bromonitrobenzene, m-bromonitrobenzene, p-bromonitrobenzene, 1-bromo-2,4-dinitrobenzene, 1-bromo-3,4-dinitrobenzene, 1-bromo-2,
4,6-trinitrobenzene, 2,3-dibromonitrobenzene, 3,4-dibromonitrobenzene, 2,4-
Dibromonitrobenzene, 2,6-dibromonitrobenzene, 4,6-dibromo-1,3-dinitrobenzene,
2,5-dibromo-1,4-dinitrobenzene, 2,
4,6-tribromonitrobenzene, 2-bromo-4-
Nitrotoluene, 2-bromo-5-nitrotoluene, 3
-Brom-2-nitrotoluene, 3-bromo-4-nitrotoluene, o-iodonitrobenzene, m-iodonitrobenzene, 1-iodo-2,4-dinitrobenzene, 1-iodo-3,4-dinitrobenzene, 3,4 ，
5-triiodonitrobenzene, 1-nitronaphthalene, 2-nitronaphthalene, dinitronaphthalene, trinitronaphthalene, tetranitronaphthalene, nitromethylnaphthalene, nitrophenylnaphthalene, halonitronaphthalene, halodinitronaphthalene, 5-nitrotetralin, 6-nitrotetralin,
5,6-dinitrotetralin, 5,7-dinitrotetralin, 5,8-dinitrotetralin, 6,7-dinitrotetralin, 3-nitro-1,2-naphthoquinone, 7-
Nitro-1,2-naphthoquinone, 3-methyl-2-nitro-1,4-naphthoquinone, 4-chloro-3-nitro-
1,2-naphthoquinone, 2,3-dichloro-5-nitro-1,4-naphthoquinone, nitroanthraquinone, p-
Examples thereof include dimethyl nitrophthalate, 4,4'-dinitrodiphenyl, 4,4'-dinitrodiphenylmethane and ethylbis (2,4-dinitrophenyl) acetate.
（４）複素環ニトロ化合物があげられる。(4) Heterocyclic nitro compounds can be mentioned.
その例としては、７−クロル−４−ニトロベンゾフラザ
ン、２−クロル−５−ニトロピリジン、２，４，５−ト
リニトロ−９−フルオレン、２，４，７−トリニトロ−
９−フルオレン、テトラニトロカルバゾールなどがあげ
られる。Examples thereof include 7-chloro-4-nitrobenzofurazan, 2-chloro-5-nitropyridine, 2,4,5-trinitro-9-fluorene, 2,4,7-trinitro-.
Examples thereof include 9-fluorene and tetranitrocarbazole.
該ニトロ化合物の使用量は、末端にアルカリ金属が結合
したジエン系重合体ゴムを製造する際に使用するアルカ
リ金属基材触媒またはジエン系重合体ゴムに後からの反
応でアルカリ金属を付加する際使用するアルカリ金属基
材触媒１モル当り、通常0.05〜10モルであり、好ましく
は0.2 〜2 モルである。The amount of the nitro compound used is such that when an alkali metal is added to the alkali metal-based catalyst or the diene polymer rubber used in the production of a diene polymer rubber having an alkali metal bonded to the terminal, in a subsequent reaction. The amount is usually 0.05 to 10 mol, preferably 0.2 to 2 mol, per mol of the alkali metal-based catalyst used.
該ニトロ化合物とアルカリ金属末端を有する活性共役ジ
エン系重合体ゴムまたはアルカリ金属が付加した共役ジ
エン系重合体ゴムとの反応は迅速に起きるので、反応温
度および反応時間は広範囲に選択できるが、一般的には
室温乃至１００℃、数秒乃至数時間である。Since the reaction between the nitro compound and the active conjugated diene-based polymer rubber having an alkali metal terminal or the conjugated diene-based polymer rubber to which an alkali metal is added occurs rapidly, the reaction temperature and the reaction time can be selected within a wide range. Specifically, the temperature is from room temperature to 100 ° C and from several seconds to several hours.
反応は、アルカリ金属含有ジエン系重合体ゴムと該ニト
ロ化合物とを接触させればよく、例えばアルカリ金属基
材触媒を用いてジエン系重合体ゴムを重合し、該重合体
ゴム溶液中に該ニトロ化合物を所定量添加する方法、ジ
エン系重合体ゴム溶液中でのアルカリ金属付加反応終了
後、引き続いて該ニトロ化合物を添加して反応させる方
法が、好ましい状態として例示できるが、この方法に限
定されるものではない。The reaction may be carried out by contacting the alkali metal-containing diene polymer rubber with the nitro compound. For example, the diene polymer rubber is polymerized using an alkali metal base catalyst, and the nitro compound is added to the polymer rubber solution. A method of adding a predetermined amount of a compound, a method of adding the nitro compound after the completion of the alkali metal addition reaction in the diene polymer rubber solution, and then reacting them can be exemplified as a preferable state, but it is not limited to this method. Not something.
得られた改質ジエン系重合体ゴムには分子末端あるいは
分子鎖中にニトロ化合物が導入されている。The obtained modified diene polymer rubber has a nitro compound introduced at the molecular end or in the molecular chain.
反応終了後、改質されたジエン系重合体ゴムは反応溶液
中から凝固剤の添加あるいはスチーム凝固など通常の溶
液重合によるゴムの製造において使用される凝固方法が
そのまま用いられ、凝固温度も何ら制限されていない。After completion of the reaction, the modified diene polymer rubber is used as it is in the coagulation method used in the production of rubber by ordinary solution polymerization such as addition of a coagulant from the reaction solution or steam coagulation, and the coagulation temperature is not limited at all. It has not been.
反応系から分離されたクラムの乾燥も通常の合成ゴムの
製造で用いられているバンドドライヤー、押し出し型の
ドライヤー等が使用でき、乾燥温度も何ら制限されな
い。The crumb separated from the reaction system can also be dried by using a band dryer, an extrusion type dryer or the like used in the usual production of synthetic rubber, and the drying temperature is not limited at all.
このようにして得られた改質ジエン系重合体ゴムは未改
質のゴムに比して反撥弾性及び低温でのＪＩＳ硬度が改
良されるので、特に自動車タイヤ用に好ましく用いられ
るが、それ以外にも靴底用、床材用、防振ゴム用などの
各種工業用原料ゴムとして使用することもできる。The modified diene-based polymer rubber thus obtained has improved impact resilience and JIS hardness at low temperatures as compared with unmodified rubber, and thus is preferably used especially for automobile tires. Also, it can be used as a raw material rubber for various industrial purposes such as shoe soles, floor materials, anti-vibration rubbers, etc.
＜実施例＞ 以下に実施例により本発明を具体的に説明するが、本発
明はこれら実施例に限定されるものではない。<Examples> The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
実施例１ 内容積１０のステンレス製重合反応器を洗浄、乾燥し
乾燥窒素で置換した後に、１，３−ブタジエン1000ｇ、
ｎ−ヘキサン4300ｇ、エチレングリコールジエチルエー
テル４０ミリモル、ｎ−ブチルリチウム（ｎ−ヘキサン
溶液）6.0 ミリモルを添加し撹拌下に５０℃で１時間重
合を行った。Example 1 A polymerization reactor made of stainless steel having an internal volume of 10 was washed, dried and replaced with dry nitrogen, and then 1000 g of 1,3-butadiene,
4300 g of n-hexane, 40 mmol of ethylene glycol diethyl ether and 6.0 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring.
重合完了後ｐ−クロルニトロベンゼンを3.0 ミリモル添
加し、撹拌下に３０分間反応させたのち、１０ミリリッ
ターのメタノールを加えて更に５分間撹拌した。After completion of the polymerization, 3.0 mmol of p-chloronitrobenzene was added, and the mixture was reacted for 30 minutes with stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（住友化学社製スミラ
イザー ＢＨＴ）を加え、ｎ−ヘキサンの大部分を蒸発
させたのち、６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumura manufactured by Sumitomo Chemical Co., Ltd.
Iser BHT) was added, and most of n-hexane was evaporated.
After that, it was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、１，２−結合単位量
（赤外分光分析法により）を測定した。The Mooney viscosity and 1,2-bond unit amount (by infrared spectroscopic analysis) of the produced polymer rubber were measured.
生成重合体ゴムのムーニー粘度は７７で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 77 and a vinyl content of 70%.
比較例１ ｐ−クロルニトロベンゼンを添加しないこと以外は実施
例１と同じ方法で重合体を得た。Comparative Example 1 A polymer was obtained by the same method as in Example 1 except that p-chloronitrobenzene was not added.
生成重合体ゴムのムーニー粘度は２３で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 23 and a vinyl content of 70%.
比較例２ ｐ−クロルニトロベンゼンを添加しないことおよびｎ−
ブチルリチウムを3.9 ミリモルとしたこと以外は実施例
１と同じ方法で重合体を得た。Comparative Example 2 No p-chloronitrobenzene was added and n-
A polymer was obtained in the same manner as in Example 1 except that butyl lithium was 3.9 mmol.
生成重合体ゴムのムーニー粘度は７７で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 77 and a vinyl content of 70%.
実施例２ 内容積１０のステンレス製重合反応器を洗浄、乾燥、
乾燥窒素で置換した後に、１，３−ブタジエン1000ｇ、
ｎ−ヘキサン4300ｇ、エチレングリコールジエチルエー
テル４０ミリモル、ｎ−ブチルリチウム（ｎ−ヘキサン
溶液）5.0 ミリモルを添加し、撹拌下に５０℃で１時間
重合を行った。Example 2 A stainless steel polymerization reactor having an internal volume of 10 was washed, dried,
After substituting with dry nitrogen, 1000 g of 1,3-butadiene,
4300 g of n-hexane, 40 mmol of ethylene glycol diethyl ether and 5.0 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring.
重合完了後クロルピクリンを5.0 ミリモル添加し、撹拌
下に３０分間反応させたのち、１０ミリリッターのメタ
ノールを加えて、更に５分間撹拌した。After the completion of the polymerization, 5.0 mmol of chloropicrin was added, and the mixture was reacted for 30 minutes with stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）を測定した。The Mooney viscosity and vinyl content (by infrared spectroscopy) of the resulting polymer rubber were measured.
生成重合体ゴムのムーニー粘度は８４で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 84 and a vinyl content of 70%.
比較例３ クロルピクリンを添加しないこと以外は実施例１と同じ
方法で重合体を得た。Comparative Example 3 A polymer was obtained in the same manner as in Example 1 except that chloropicrin was not added.
生成重合体ゴムのムーニー粘度は４６で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 46 and a vinyl content of 70%.
比較例４ クロルピクリンを添加しないことおよびｎ−ブチルリチ
ウムを3.8 ミリモルとしたこと以外は実施例１と同じ方
法で重合体を得た。Comparative Example 4 A polymer was obtained in the same manner as in Example 1 except that chloropicrin was not added and n-butyllithium was 3.8 mmol.
生成重合体ゴムのムーニー粘度は８４で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 84 and a vinyl content of 70%.
実施例３ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、乾燥窒素で置換した後に、１，３−ブタジエン1000
ｇ、ｎ−ヘキサン4300ｇ、エチレングリコールジエチル
エーテル４０ミリモル、ｎ−ブチルリチウム（ｎ−ヘキ
サン溶液）6.4 ミリモルを添加し、撹拌下に５０℃で１
時間重合を行った。Example 3 A stainless steel polymerization reactor having an internal volume of 10 was washed, dried, and purged with dry nitrogen.
g, 4300 g of n-hexane, 40 mmol of ethylene glycol diethyl ether, and 6.4 mmol of n-butyllithium (n-hexane solution) were added, and the mixture was stirred at 50 ° C. for 1 hour.
Polymerization was carried out for a time.
重合完了後ｐ−ニトロフタル酸ジメチルを3.2 ミリモル
添加し、撹拌下に３０分間反応させたのち、１０ミリリ
ッターのメタノールを加えて更に５分間撹拌した。After the completion of the polymerization, 3.2 mmol of dimethyl p-nitrophthalate was added, and the mixture was reacted for 30 minutes with stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）を測定した。The Mooney viscosity and vinyl content (by infrared spectroscopy) of the resulting polymer rubber were measured.
生成重合体ゴムのムーニー粘度は５６で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 56 and a vinyl content of 70%.
比較例５ ｐ−ニトロフタル酸ジメチルを添加しないこと以外は実
施例３と同じ方法で重合体を得た。Comparative Example 5 A polymer was obtained in the same manner as in Example 3 except that dimethyl p-nitrophthalate was not added.
生成重合体ゴムのムーニー粘度は１７で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 17 and a vinyl content of 70%.
比較例６ ｐ−ニトロフタル酸ジメチルを添加しないことおよびｎ
−ブチルリチウムを4.5 ミリモルとしたこと以外は実施
例３と同じ方法で重合体を得た。Comparative Example 6 No addition of dimethyl p-nitrophthalate and n
A polymer was obtained in the same manner as in Example 3, except that the amount of -butyllithium was 4.5 mmol.
生成重合体ゴムのムーニー粘度は５６で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 56 and a vinyl content of 70%.
実施例４ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、乾燥窒素で置換した後に、１，３−ブタジエン750
ｇ、スチレン250 ｇ、ｎ−ヘキサン4300ｇ、テトラヒド
ロフラン２３ｇ、ｎ−ブチルリチウム（ｎ−ヘキサン溶
液）6.4 ミリモルを添加し、撹拌下に５０℃で１時間重
合を行った。重合完了後ｐ−クロルニトロベンゼンを3.
2 ミリモル添加し、撹拌下に３０分間反応させたのち、
１０ミリリッターのメタノールを加えて、更に５分間撹
拌した。Example 4 A polymerization reactor made of stainless steel with an internal volume of 10 was washed, dried, and purged with dry nitrogen.
g, 250 g of styrene, 4300 g of n-hexane, 23 g of tetrahydrofuran, and 6.4 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring. After completion of polymerization, p-chloronitrobenzene was added to 3.
After adding 2 mmol and reacting for 30 minutes under stirring,
10 milliliter of methanol was added, and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）およびスチレン含量（屈折率法により）
を測定した。Mooney viscosity, vinyl content (by infrared spectroscopy) and styrene content (by refractive index method) of the resulting polymer rubber
Was measured.
生成重合体ゴムのムーニー粘度は７７、スチレン含量は
２５％、ビニル含量は４０％であった。The produced polymer rubber had a Mooney viscosity of 77, a styrene content of 25% and a vinyl content of 40%.
比較例７ ｐ−クロルニトロベンゼンを添加しないこと以外は実施
例４と同じ方法で重合体を得た。Comparative Example 7 A polymer was obtained in the same manner as in Example 4, except that p-chloronitrobenzene was not added.
生成重合体ゴムのムーニー粘度は２３、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 23, a styrene content of 25% and a vinyl content of 40%.
比較例８ ｐ−クロルニトロベンゼンを添加しないことおよびｎ−
ブチルリチウムを4.0 ミリモルとしたこと以外は実施例
４と同じ方法で重合体を得た。Comparative Example 8 No addition of p-chloronitrobenzene and n-
A polymer was obtained in the same manner as in Example 4 except that the amount of butyllithium was 4.0 mmol.
生成重合体ゴムのムーニー粘度は７７、スチレン含量は
２５％、ビニル含量は４０％であった。The produced polymer rubber had a Mooney viscosity of 77, a styrene content of 25% and a vinyl content of 40%.
実施例５ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、乾燥窒素で置換した後に、１，３−ブタジエン750
ｇ、スチレン250 ｇ、ｎ−ヘキサン4300ｇ、テトラヒド
ロフラン４０ミリモル、ｎ−ブチルリチウム（ｎ−ヘキ
サン溶液）5.2 ミリモルを添加し、撹拌下に５０℃で１
時間重合を行った。Example 5 A polymerization reactor made of stainless steel having an internal volume of 10 was washed, dried, and purged with dry nitrogen, and then 1,3-butadiene 750 was used.
g, styrene 250 g, n-hexane 4300 g, tetrahydrofuran 40 mmol, n-butyllithium (n-hexane solution) 5.2 mmol, and the mixture was stirred at 50 ° C. for 1 hour.
Polymerization was carried out for a time.
重合完了後、クロルピクリンを5.2 ミリモル添加し、撹
拌下に３０分間反応させたのち、１０ミリリッターのメ
タノールを加えて更に５分間撹拌した。After completion of the polymerization, chloropicrin (5.2 mmol) was added, and the mixture was reacted for 30 minutes with stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）およびスチレン含量（屈折率法により）
を測定した。Mooney viscosity, vinyl content (by infrared spectroscopy) and styrene content (by refractive index method) of the resulting polymer rubber
Was measured.
生成重合体ゴムのムーニー粘度は８４、スチレン含量は
２５％、ビニル含量は４０％であった。The produced polymer rubber had a Mooney viscosity of 84, a styrene content of 25% and a vinyl content of 40%.
比較例９ クロルピクリンを添加しないこと以外は実施例５と同じ
方法で重合体を得た。Comparative Example 9 A polymer was obtained in the same manner as in Example 5, except that chloropicrin was not added.
生成重合体ゴムのムーニー粘度は４６、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 46, a styrene content of 25% and a vinyl content of 40%.
比較例１０ クロルピクリンを添加しないことおよびｎ−ブチルリチ
ウムを3.8 ミリモルとしたこと以外は実施例５と同じ方
法で重合体を得た。Comparative Example 10 A polymer was obtained in the same manner as in Example 5 except that chloropicrin was not added and n-butyllithium was 3.8 mmol.
生成重合体ゴムのムーニー粘度は８４、スチレン含量は
２５％、ビニル含量は４０％であった。The produced polymer rubber had a Mooney viscosity of 84, a styrene content of 25% and a vinyl content of 40%.
実施例６ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、乾燥窒素で置換した後に１，３−ブタジエン750
ｇ、スチレン250 ｇ、ｎ−ヘキサン4300ｇ、テトラヒド
ロフラン２３ｇ、ｎ−ブチルリチウム（ｎ−ヘキサン溶
液）7.2 ミリモルを添加し、撹拌下に５０℃で１時間重
合を行った。Example 6 A stainless steel polymerization reactor having an internal volume of 10 was washed, dried, and purged with dry nitrogen, and then 1,3-butadiene 750 was used.
g, styrene 250 g, n-hexane 4300 g, tetrahydrofuran 23 g, and n-butyllithium (n-hexane solution) 7.2 mmol were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring.
重合完了後ｐ−ニトロフタル酸ジメチルを3.6 ミリモル
添加し、撹拌下に30分間反応させたのち、１０ミリリッ
ターのメタノールを加えて、更に５分間撹拌した。After completion of the polymerization, 3.6 mmol of dimethyl p-nitrophthalate was added, the mixture was reacted for 30 minutes with stirring, 10 ml of methanol was added, and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し５ｇの２，６−ジ
−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Thereafter, the contents of the polymerization reactor were taken out and 5 g of 2,6-di-
-T-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）およびスチレン含量（屈折率法により）
を測定した。Mooney viscosity, vinyl content (by infrared spectroscopy) and styrene content (by refractive index method) of the resulting polymer rubber
Was measured.
生成重合体ゴムのムーニー粘度は５６、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 56, a styrene content of 25% and a vinyl content of 40%.
比較例１１ ｐ−フタル酸ジメチルを添加しないこと以外は実施例６
と同じ方法で重合体を得た。Comparative Example 11 Example 6 except that p-dimethyl phthalate was not added.
A polymer was obtained by the same method as described above.
生成重合体ゴムのムーニー粘度は１７、スチレン含量は
２５％、ビニル含量は４０％であった。The produced polymer rubber had a Mooney viscosity of 17, a styrene content of 25% and a vinyl content of 40%.
比較例１２ ｐ−ニトロフタル酸ジメチルを添加しないことおよびｎ
−ブチルリチウムを4.8 ミリモルとしたこと以外は実施
例６と同じ方法で重合体を得た。Comparative Example 12 No dimethyl p-nitrophthalate was added and n
A polymer was obtained by the same method as in Example 6 except that butyllithium was 4.8 mmol.
生成重合体ゴムのムーニー粘度は５６、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 56, a styrene content of 25% and a vinyl content of 40%.
（配合・加硫ゴム物性） 実施例１〜６および比較例１〜１２の生成重合体ゴムを
第１表の配合処方に従い、ロール上で混練し配合ゴムを
得、これを１６０℃×３０分の条件でプレス加硫した。(Physical Properties of Compounded / Vulcanized Rubber) The polymer rubbers produced in Examples 1 to 6 and Comparative Examples 1 to 12 were kneaded on a roll according to the compounding recipe shown in Table 1 to obtain a compounded rubber, which was heated at 160 ° C. for 30 minutes. Press vulcanization was carried out under the conditions.
加硫ゴムの反撥弾性はリュプケレジリエンステ スターを用いて６０℃で測定した。ＪＩＳ硬度はＪＩＳ
Ｋ６３０１により−２０℃で測定した。The impact resilience of vulcanized rubber is It measured at 60 degreeC using the star. JIS hardness is JIS
It was measured by K6301 at -20 ° C.
これらの結果を第２表に示す。この結果から、本発明の
重合体は、ニトロ化合物を添加しないこと以外は本発明
の重合体と同一方法で得た重合体及び本発明の重合体と
ムーニー粘度を同一にしたニトロ化合物を含有しない重
合体に比べて反撥弾性が著しく高く、かつ低温でのＪＩ
Ｓ硬度が著しく低いことがわかる。The results are shown in Table 2. From this result, the polymer of the present invention does not contain a nitro compound having the same Mooney viscosity as that of the polymer of the present invention or the polymer of the present invention except that the nitro compound is not added. Repulsive elasticity is significantly higher than that of polymer and JI at low temperature
It can be seen that the S hardness is extremely low.
実施例７および比較例１３ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、スチレン−ブタジエン共重合体（ムーニー粘度５
１、スチレン含量２５％、ビニル含量４０％）500 ｇ、
ｎ−ヘキサン4300ｇを仕込み、撹拌溶解させた。次にｎ
−ブチルリチウム（ｎ−ヘキサン溶液）6.4 ミリモル及
びテトラメチルエチレンジアミン6.4 を添加し、７０℃
で１時間反応させた。Example 7 and Comparative Example 13 A stainless steel polymerization reactor having an internal volume of 10 was washed and dried to obtain a styrene-butadiene copolymer (Moonie viscosity 5
1, styrene content 25%, vinyl content 40%) 500 g,
4300 g of n-hexane was charged and dissolved with stirring. Then n
-Butyllithium (n-hexane solution) 6.4 mmol and tetramethylethylenediamine 6.4 were added, and the temperature was 70 ° C.
And reacted for 1 hour.
次にｐ−クロルニトロベンゼンを3.2 ミリモル添加し、
撹拌下に30分間反応させたのち、１０ミリリッターのメ
タノールを加えて更に５分間撹拌した。Next, 3.2 mmol of p-chloronitrobenzene was added,
After reacting for 30 minutes under stirring, 10 milliliter of methanol was added and stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。得られた重合体のムー
ニー粘度は６６であった。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours. The obtained polymer mu
The knee viscosity was 66.
次に該重合体について実施例１と同様の方法にて配合、
加硫ゴム物性を測定した。Next, the polymer was blended in the same manner as in Example 1,
The vulcanized rubber physical properties were measured.
また比較のため、変性前の前記スチレン−ブタジエン共
重合体（ムーニー粘度５１、スチレン含量２５％、ビニ
ル含量４０％）について同様の方法にて配合、加硫ゴム
物性を測定し比較例１３とした。For comparison, the styrene-butadiene copolymer before modification (Moonie viscosity 51, styrene content 25%, vinyl content 40%) was compounded by the same method, and the physical properties of the vulcanized rubber were measured and set as Comparative Example 13. .
これらの結果を第２表に示した。The results are shown in Table 2.
＜発明の効果＞ 以上述べたように、本発明によれば反撥弾性を高め、低
温でのＪＩＳ硬度を低減するジエン系共重合体ゴムの改
質方法を提供することができる。<Effects of the Invention> As described above, according to the present invention, it is possible to provide a method for modifying a diene copolymer rubber that enhances impact resilience and reduces JIS hardness at low temperatures.
Claims (1)
くは共役ジエンモノマーと芳香族ビニルモノマーとをア
ルカリ金属系触媒を用いて重合を行うことにより得られ
るアルカリ金属末端を有する活性共役ジエン系重合体ゴ
ム、または、炭化水素溶媒中で重合体鎖中に共役ジエン
単位を有するジエン系重合体ゴムとアルカリ金属系触媒
とを反応させることにより得られるアルカリ金属が付加
された共役ジエン系重合体ゴムに対して、ニトロ化合物
を反応させてなることを特徴とする変性ジエン系重合体
ゴムの製造方法。1. An active conjugated diene polymer rubber having an alkali metal terminal, which is obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an alkali metal catalyst. Or, for a conjugated diene-based polymer rubber to which an alkali metal has been added, which is obtained by reacting a diene-based polymer rubber having a conjugated diene unit in the polymer chain in a hydrocarbon solvent with an alkali-metal-based catalyst. A method for producing a modified diene polymer rubber, which comprises reacting a nitro compound.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28709186A JPH0653766B2 (en) | 1986-12-01 | 1986-12-01 | Method for producing modified diene polymer rubber |
| DE3789203T DE3789203T2 (en) | 1986-12-01 | 1987-12-01 | Process for the preparation of modified rubber-diene polymers. |
| CA000553234A CA1310787C (en) | 1986-12-01 | 1987-12-01 | Process for preparing modified diene polymer rubbers |
| EP87117741A EP0270071B1 (en) | 1986-12-01 | 1987-12-01 | Process for preparing modified diene polymer rubbers |
| US07/415,380 US4957976A (en) | 1986-12-01 | 1989-09-29 | Process for preparing diene polymer rubbers |
| US07/501,700 US5015692A (en) | 1986-12-01 | 1990-03-30 | Process for preparing modified diene polymer rubbers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28709186A JPH0653766B2 (en) | 1986-12-01 | 1986-12-01 | Method for producing modified diene polymer rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63139902A JPS63139902A (en) | 1988-06-11 |
| JPH0653766B2 true JPH0653766B2 (en) | 1994-07-20 |
Family
ID=17712934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28709186A Expired - Lifetime JPH0653766B2 (en) | 1986-12-01 | 1986-12-01 | Method for producing modified diene polymer rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653766B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10053526B2 (en) | 2014-07-09 | 2018-08-21 | Ube Industries, Ltd. | Catalyst for conjugated diene polymerization, conjugated diene polymer, modified conjugated diene polymer, polybutadiene, and compositions comprising foregoing |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4080063B2 (en) * | 1998-06-15 | 2008-04-23 | 住友ゴム工業株式会社 | Rubber composition |
| JP2000001575A (en) * | 1998-06-15 | 2000-01-07 | Sumitomo Rubber Ind Ltd | Rubber composition containing modified diene rubber |
| EP3204429B1 (en) * | 2014-10-07 | 2018-09-05 | Bridgestone Corporation | Method for producing polydienes and polydiene copolymers with reduced cold flow |
-
1986
- 1986-12-01 JP JP28709186A patent/JPH0653766B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10053526B2 (en) | 2014-07-09 | 2018-08-21 | Ube Industries, Ltd. | Catalyst for conjugated diene polymerization, conjugated diene polymer, modified conjugated diene polymer, polybutadiene, and compositions comprising foregoing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63139902A (en) | 1988-06-11 |
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